KR100984669B1 - The preparation method for silver bonded or substitution hydroxyaphatite with electric ion exchange - Google Patents

Abstract

The silver produced by using a water-soluble silver such as silver nitrate, silver chloride, or the like is substituted with hydroxyapatite substituted by silver, and the silver can be substituted by an electrolysis method using an acid that can control and substitute pure silver. A method for preparing hydroxyapatite that is deposited is disclosed. The silver-substituted and deposited hydroxyapatite prepared by the present invention confers more functions than the conventional hydroxyapatite, thus enabling many applications in new fields as well as in industrial and medical applications.

Description

The preparation method for silver bonded or substitution hydroxyaphatite with electric ion exchange}

The present invention relates to a method for producing hydroxyapatite, and more particularly, to a method for preparing hydroxyapatite in which silver is substituted or deposited. In particular, the present invention relates to a method for preparing hydroxyapatite which is filtered and dried after substitution or deposition of silver to hydroxyapatite by electrolysis.

Hydroxyapatite is a compound of calcium and phosphorus, and may have a similar structure such as amorphous tricalcium phosphate, alpha-tricalcium phosphate, beta- tricalcium phosphate, fluoraphatite, hydroxyfluoraphatite, etc. according to heat or substituent change. These hydroxyapatites are used as food additives, artificial bone and tooth materials, abrasives, feed additives, toothpaste additives, polymer additives, ceramics, and the like. In general, a method of replacing silver with a calcium phosphate compound has been produced through drying and calcining by substitution or impregnation in an aqueous solution with silver nitrate or silver halide. However, it is difficult to control silver content of silver-substituted hydroxyapatite made of water-soluble silver such as halogen and nitric acid, and it is difficult to prepare calcium phosphate compound substituted or deposited with pure silver ions. Was required.

Accordingly, an object of the present invention is to solve the problems of the prior art and to provide a hydroxyapatite which can more easily deposit or substitute pure silver than the conventional method by adjusting the content of silver, thereby It is to provide a method for producing hydroxyapatite substituted or deposited silver, which can add antibacterial and bactericidal properties.

The present invention to achieve the object of the present invention as described above;

As a method for preparing hydroxy apatite substituted or deposited silver,

Preparation of silver-substituted or deposited hydroxyapatite, which comprises dispersing or depositing the hydroxyapatite compound in a vessel containing water or an organic solution, and then electrolytically displacing or depositing silver into the hydroxyapatite, filtering and drying. Provide a method.

In the above, when dispersing the hydroxyapatite, it is preferable to disperse the hydroxyapatite alone or by adding at least one additive of an acid, an alcohol, a polymer, an enzyme and an antioxidant for dispersion and effective ion transfer. Apatite alone or used for dispersion and effective ion transfer.

In addition, the electrolysis method is preferably made by sending a current to the electrode connecting the silver to the anode and / or cathode in the container.

In the above, when dispersing the compound of hydroxyapatite in the container hydroxyapatite is to disperse 1 ~ 100wt%, preferably 20 ~ 60wt% compared to water or solution, 20wt% is inefficient, 60wt If it is more than%, dispersion becomes difficult.

In addition, the hydroxyapatite compound is a compound of calcium and phosphorus, and may include the same or similar structure of at least one of amorphous tricalcium phosphate, alpha-tricalcium phosphate, beta-tricalcium phosphate, fluoraphatite, and hydroxyfluoraphatite depending on the substituent change. , The electrolysis is preferably carried out while heating to 10 ~ 100 ℃ or after heating to the temperature, if less than 10 ℃ is less than the transfer capacity of ions, if more than 100 ℃ evaporation of water is difficult to electrolysis difficult Because of this.

In addition, the filter and drying in the above is preferably carried out at 80 ~ 200 ℃ for effective evaporation of water or solvent, and then further high temperature heat treatment of 200 ~ 1500 ℃ for the removal of impurities or effective settling of ions. have.

In addition, the additive is preferably added in an amount of 0.01 to 15wt% based on the weight of water or the organic solution.

In addition, one side of the electrode during the electrolysis of the present invention may use one selected from copper, tin, gold, aluminum, zinc or iron having a purity of 99% or more.

In addition, the electrolysis in the present invention is performed while stirring at 5 ~ 300rpm for efficient dispersion of the powder, the additive is an inorganic acid selected from hydrochloric acid, sulfuric acud, phosphoric acid; acetic acid, adipic acid, maleic acid, malic acid, malonic acid, sorbic acid, tartaric acid, citric acid, lactic acid, succinic acid, fumaric acid, estearic acid, acetylaslicylic acid, salicylic acid, benzoic acid, glycolic acid, glutaric acid , organic acid selected from gluconolactone; Fatty acids which are carboxylic acids of C ₂ -C ₂₂ ; a polymer selected from polyacrylic acid, cellulose, biopolymer and glucose; enzyme ; Antioxidant which is butylated hydroxyanisole (BHA); Butylated hydroxytoluene (BHT); vitamin A; vitamin C; natural extract antioxidant; and alcohol (having a range of C ₁ -C ₂₂ and having an OH group having one or two or more substituents).

As described above, according to the present invention, by replacing and depositing hydroxyapatite silver using an electrolysis method using an acid, the conventional hydroxyapatite is added by adding antibacterial and bactericidal properties of silver to the function of hydroxyapatite. Hydroxyapatite can be prepared that can impart even more functions. Also, in the process, pure silver can be substituted and deposited, and the content of substituted silver can be controlled more effectively than conventional water soluble silver such as silver nitrate or silver chloride. In general, the use of silver for antibacterial or bactericidal is in the form of silver ions, colloids or nano oxides, but the use of polymers and medical materials is unstable or problematic in processability, but the silver produced by the method of the present invention is deposited. And the substituted hydroxyapatite is easy to be powdered and coated, etc., it will be possible not only for industrial use and medical use, but also for many applications in new fields.

As described above, according to the present invention, a method of dispersing and depositing a hydroxyapatite compound, which is prepared by any method, granulated or powdered, in water or other organic solution and then using an electrolysis method is provided. do. In other words, 1-100wt% of the hydroxyapatite, preferably 20-50wt% of the hydroxyapatite is dispersed in water or an organic solution, and then a silver is connected to the anode and the cathode by an electrolysis method to send a current. Stable substitution or deposition of silver ions on calcium of the compound. When dispersing the hydroxyapatite compound in water or other organic solutions, various inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, etc.), organic acids (adipic acid, maleic acid, malic acid, malonic acid, sorbic acid, tartaric acid, citric acid, lactic acid, succinic acid, fumaric acid, estearic acid, acetylsalicylic acid, salicylic acid, benzoic acid, glycolic acid, glutaric acid, gluconic acid, gluconolactone, etc.) and fatty acids (carboxylic acids of C ₂ -C ₂₂ ) It can be used by adding 0.001-50 wt% by weight. At this time, polymer (polyacrylic acid, cellulose, biopolymer, glucose, etc.), enzyme (enzyme), antioxidant (BHA (butylated hydroxyanisole), BHT (butylated hydroxytoluene), Vitamin A, Vitamin C, natural extract antioxidant) and various alcohols ( C ₁ -C ₂₂ range, OH group having one or two or more substituents, etc. can be used by dispersing or dissolving a certain amount (0.001-50 wt% by weight of water) alone or in two or more materials together It is then electrolyzed after heating to room temperature or below 100 ° C or while heating. In addition, the voltage used for electrolysis is usually a variable current supply (0-220V) that can be adjusted according to the amount of silver ionization. Silver (Ag) is a high purity silver plate (silver plate) with a purity of 99.9% or more. And the like were used. In order to substitute or deposit a stabilized form in an aqueous solution or an organic solution, only a hydroxyapatite compound may be dispersed in an aqueous solution or an organic solution to supply current to dye or deposit silver, and various types of acids, alcohols, Organic matters such as surfactants were treated alone or in mixture with a calcium phosphate compound in advance (0.01-50 wt%) in a solution (preferably 0.5-15 wt%), and then silver (Ag) by electrolysis. Ions may be substituted and deposited. At this time, in order to induce effective substitution and deposition, the hydroxyapatite compound may be dispersed while appropriately stirring (5-300 rpm), and the temperature of the aqueous solution or the organic solution is heated (100 ° C.) using a heating plate during electrolysis. You can also proceed).

Example

Put 2000 ml of tertiary distilled water into a beaker of 300 ml of aqueous solution (mL) and connect a silver plate of size 2x 1 cm and purity of 99.99 to distilled water with 5 mm gap between the positive and negative electrodes. do. Hydroxyapatite (molecular weight 502g, CaO 51-54%, pH 6.8Min, 400mesh 99% thru, = water content 3%) is slowly dispersed 15g in distilled water. Here, the dispersion of acetic acid by concentration, and after the dispersion is completed, the experiments according to the time and acid concentration while changing the current using a current supply (Power Supply) is carried out as shown in Table 1. After passing the current by time, the filter was filtered and the sample was dried for 10 hours in an oven at 105 ° C. The silver content of the samples was measured by EDS (Dispersive X-ray Spectroscopy) as shown in Fig. 1 to show two representative views. It was. The substitution of silver and the change of deposited content according to the reaction time of the experiment of Table 1 are shown in FIG. 2A, and the substitution and deposition of silver with the concentration of acetic acid added in the reaction of the same time are shown in FIG. 2B.

Table 1 Silver Substitution and Deposition Experiments of Hydroxyaphatite and Their Content

1 is a representative diagram of silver substituted and deposited EDS (Dispersive X-ray Spectroscopy) of Hydroxyaphatite using an electrolysis method.

Figure 2a is a graph showing the substitution and deposition of silver with the reaction time.

Figure 2b is a graph showing the substitution and deposited content of silver with the concentration of acid.

Claims (10)

As a method for preparing hydroxy apatite substituted or deposited silver, After dispersing the hydroxyapatite compound in a container containing water or an organic solution, silver is substituted or deposited on the hydroxyapatite by electrolysis, filtering and drying, Manufacturing method. The method for producing silver-substituted or deposited hydroxyapatite according to claim 1, wherein the hydroxyapatite is dispersed by adding at least one additive of an acid, an alcohol, a polymer, an enzyme and an antioxidant. . The method of claim 1, wherein the electrolysis method is characterized in that the current is sent to the electrode connecting the silver to the positive electrode and / or the negative electrode in the container, silver substituted or deposited hydroxyapatite method. The method of claim 1, wherein when dispersing the compound of hydroxyapatite in the container, the hydroxyapatite is 1 to 100wt% of water or a solution, wherein the hydroxyapatite is substituted or deposited. The hydroxyapatite compound is a compound of calcium and phosphorus, and according to the substituent change, amorphous tricalcium phosphate, alpha-tricalcium phosphate, beta-tricalcium phosphate, fluoraphatite, hydroxyfluoraphatite A method for producing hydroxyapatite substituted or deposited silver, characterized in that it comprises the same or similar structure to one or more of the structure. The method of claim 3, wherein the electrolysis is performed while heating to 10 to 100 ° C. or after heating to the temperature. The method for producing hydroxyapatite substituted or deposited according to claim 1, wherein the filter and drying are performed at 80 ° C. to 200 ° C., and then further subjected to high temperature heat treatment at 200 ° C. to 1500 ° C. 6. The method of claim 2, wherein the additive is added in an amount of 0.01 to 15 wt% based on the weight of water or the organic solution. The method of claim 3, wherein one side of the electrode is one selected from copper, tin, gold, aluminum, zinc, or iron. The method according to claim 1 or 2, wherein the electrolysis is performed while stirring at 5 to 300 rpm, and the additive is an inorganic acid selected from hydrochloric acid, sulfuric acud, and phosphoric acid; acetic acid, adipic acid, maleic acid, malic acid, malonic acid, sorbic acid, tartaric acid, citric acid, lactic acid, succinic acid, fumaric acid, estearic acid, acetylaslicylic acid, salicylic acid, benzoic acid, glycolic acid, glutaric acid , organic acid selected from gluconolactone; Fatty acids which are carboxylic acids of C ₂ -C ₂₂ ; a polymer selected from polyacrylic acid, cellulose, biopolymer and glucose; enzyme ; Antioxidant which is butylated hydroxyanisole (BHA); Silver is characterized in that it is selected from butylated hydroxytoluene; vitamin A; vitamin C; natural extract antioxidant; and alcohol (having a range of C ₁ -C ₂₂ and the OH group having one or more substituents) Process for preparing substituted or deposited hydroxyapatite.

Images